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By W. K. Lewis, Lombard Squires, W. I. Thompson

The authors presented an article2† last year on colloidal properties of clay suspensions in which they attempted to sustain the position that the behavior of clay suspensions is due primarily to the mechanical interference of the platy particles, the nature and extent of the interference being profoundly influenced by the character of the surfaces of the particles, which in turn is determined primarily by the nature and amount of adsorbed foreign materials held on the surface of the particles by forces which are predominantly chemical in type. The following discussion is a continuation of that article to extend these same interpretative points of view to the behavior of clay gels. Insight into the mechanism of gelation is certainly of outstanding importance in the handling of drilling muds. In the former article it was suggested that the thin, flat plates that constitute the ultimate clay particles may build up aggregates by the overlapping of the ultimate plates face to face much longer and perhaps also much wider than the ultimate plates themselves, but not appreciably thicker. Exhaustive microscopic examinations of characteristic clays show no tendency for the larger particles, clearly visible under the microscope, to orient themselves in this way. It is true that the gelation of the clays is due primarily to the smallest particles, unresolvable other than by the ultramicroscope, so that the possibility of the deve1opment by them of an overlapping structure is not excluded. Furthermore, as one approaches the limit of resolving power of the microscope, the difficulty of observing accurately the shapes and relative positions of particles incresses excessively. However, in the absence of any observable tendency toward overlapping orientation of the large, visible particles, one hesitates to ascribe such a tendency to the smaller particles beyond the range of visibility. Should it develop that one must exclude the assumption of overlapping orientation, the explanations offered in the previous article are changed in only one respect; namely, one would now have to assume that the ultimate particles themselves have length, and probably also width, very large in comparison with their thickness.

Jan 1, 1936

By Lombard Squires, W. K. Lewis, W. I. Thompson

The authors presented an article2† last year on colloidal properties of clay suspensions in which they attempted to sustain the position that the behavior of clay suspensions is due primarily to the mechanical interference of the platy particles, the nature and extent of the interference being profoundly influenced by the character of the surfaces of the particles, which in turn is determined primarily by the nature and amount of adsorbed foreign materials held on the surface of the particles by forces which are predominantly chemical in type. The following discussion is a continuation of that article to extend these same interpretative points of view to the behavior of clay gels. Insight into the mechanism of gelation is certainly of outstanding importance in the handling of drilling muds. In the former article it was suggested that the thin, flat plates that constitute the ultimate clay particles may build up aggregates by the overlapping of the ultimate plates face to face much longer and perhaps also much wider than the ultimate plates themselves, but not appreciably thicker. Exhaustive microscopic examinations of characteristic clays show no tendency for the larger particles, clearly visible under the microscope, to orient themselves in this way. It is true that the gelation of the clays is due primarily to the smallest particles, unresolvable other than by the ultramicroscope, so that the possibility of the deve1opment by them of an overlapping structure is not excluded. Furthermore, as one approaches the limit of resolving power of the microscope, the difficulty of observing accurately the shapes and relative positions of particles incresses excessively. However, in the absence of any observable tendency toward overlapping orientation of the large, visible particles, one hesitates to ascribe such a tendency to the smaller particles beyond the range of visibility. Should it develop that one must exclude the assumption of overlapping orientation, the explanations offered in the previous article are changed in only one respect; namely, one would now have to assume that the ultimate particles themselves have length, and probably also width, very large in comparison with their thickness.

Jan 1, 1936

By Frederic H. Lahee

After abandoning two dry holes, on the Mrs. Daisy Bradford land, C. M. Joiner finally completed his No. 3 on Sept. 8, 1930, at a total depth of 3592 ft. This well is 735 miles somewhat north of west of the town of Henderson, in Rusk County. Between Oct. 2 and Oct. 6, this well made numerous heads which indicated that it would produce about 300 bbl. daily. By Nov. 27, two dry holes,' completed near the Joiner well, taken in conjunction with the small production from this well, served to dampen any enthusiasm among those who hoped for a major pool; but by December 18 three other producers had been completed. On Dec. 28, 1930, E. W. Bateman's Lois Della Crim No. 1 drilled itself in with an estimated daily yield of between 10,000 and 15,000 bbl. from a depth of 3650 ft. This well, 10 miles north of the Joiner well, also in Rusk County, initiated the leasing campaign that led to the later orgy of drilling. On Jan. 25, 1931, Moncrief, Farrell and others completed their J. K. Lathrop 1 as another big producer, 7 miles east of Gladewater in Gregg County and 14 miles N. 20" E. from the Bateman Crim well. The Lathrop well, 3574 ft. deep, flowed 320 bbl. in 1 hr. through a ½in. choke. The first well completed in Smith County was Cook No. 1, drilled by Guy Lewis et al. in the James Jordan Survey, 4.7 miles west of the Joiner discovery well. On Mar. 30, 1931, it flowed 137 bbl. in 33 min, through a ¾-in. choke. The top of the pay sand was found at 3672 ft. Finally, in Upshur County, on May 5, the Mudge Oil Co. et al. completed the Richardson No. 1, which flowed 274 bbl. through a 4 2/64-in. choke in 2 hr. This well is 4 miles northwest of the Lathrop producer. Development It is unnecessary to give a lengthy description of the rapid development of the area discovered in these five far-separated wells, or to discuss the speculations offered as to whether there were several pools or only one.

Jan 1, 1932

By D. Harker, W. E. Seymour

CERTAIN alloys of iron and nickel, when rolled and annealed, possess a preferred crystal orientation: (001) in the rolling plane and [loo] in the rolling direction, when recrystallized at 850" to 1050°C after approximately 98 pct cold reduction. Since the preferred orientation makes a direction of easiest magnetization coincide with the rolling direction, these alloys, especially a 50 pct iron in nickel alloy, have found wide application in the electrical industry' for choke coils and special types of transformers. The rate of the recrystallization reaction was studied at temperatures ranging from 500° to 600°C. The heat of activation for the reaction was calculated from the observed rates, and crystal orientation determinations were made before and after re-crystallization. A vacuum melted iron-nickel alloy* analyzing 49.6 pct nickel, 0.018 pct carbon, and 0.30 pct manganese was used for the experiments. The alloy was cold-rolled 98 pct into strips 1/2 in. wide by 0.002 in. thick. Specimens 1 in. long were sealed under a vacuum (approximately 10-8 mm Hg) in 1/2 in. ID pyrex glass tubes. For heat treatment these tubes were fastened to Nicrohm wires and submerged in a molten salt bath controlled to ±2°C. (The maximum measurement error was within 3°C.) The time at temperature was varied logarithmically from one sample to another, and runs were made at 500°, 525", 550" and 575°C. A molten lead bath was used for a run at 600°C which was controlled to the same accuracy. To determine the extent of recrystallization after a particular time at a given temperature, a method was used suggested by the work of Decker, Asp, and Harker.3,4 This method employs an X-ray spectrometer whereby X rays are diffracted from crystallites whose diffracting atom planes are parallel to the rolling plane of the specimen. The intensities of the diffracted rays are measured by a Geiger counter. The counter can be rotated through a range of angle, and can be motor driven through this range at a speed of 2" per min. The measured intensities are plotted vs. angle by a potentiometer recorder. In a 50 pct iron-nickel alloy it was found that only (200) reflections were obtained from the rolling plane with recrystallized material, and that only (220) reflections were obtained from the rolling plane with unrecrystallized material. No other reflections were obtained under these conditions over a range of Bragg angle of 0 to 45" using either type of specimen. As a consequence, the intensity of the (200) reflections from the rolling plane was taken to indicate the amount of recrystallized ma-terial present in a specimen, and the corresponding intensity of the (220) reflections was taken to indicate the amount of unrecrystallized material present. To insure flatness and proper alignment of the reflecting specimen in the spectrometer, the sample was laid in a slot 1/2 in. wide x 0.001 in. deep which was machined in a 3/4x2x1/2 in. steel carrier. The specimen then was taped down with cellophane tape. This steel cradle was mounted vertically in the specimen holder of the spectrometer so that the bottom edge of the carrier rested against a horizontal shoulder. Intensity data used in plotting the percent of recrystallized material vs. time at temperature were obtained by directly counting the diffracted beam of nickel filtered copper Ka radiation used throughout the work. The X-ray spectrometer was employed also in obtaining pole figure data to be used for orientation determinations. At the beginning of this investigation a transmission pole figure holder was used." As a thickness of 0.002 in. of this alloy was found to be opaque to the copper Ka radiation, it was necessary to reduce the thickness of the pole figure specimen. A cold-worked sample was etched in a 50 pct HCl solution for 5 min and was found to transmit a

Jan 1, 1951

By P. Chiotti, J. T. Mason

Thermal, X-ray, metallographic, and resistivity data were obtained to establish the phase diagram for the Yb-Zn system. Six intermetallic compounds and five eutectics have been identified. The compounds position at 695°C. No evidence for the compound YbZn,, was observed. Whether this compound is stabilized or inhibited by small amounts of impurities is uncertain. SEVERAL aspects of the Yb-Zn system have been reported in the literature. Much of this work deals with the crystallographic identification of some of the compounds. The YbZn compound has been reported by Iandelli and palenzonal and the YbZn, structure and thermal data for the composition range between YbZn and Yb3Znll have been reported by Michel et al. A compound of uncertain stoichiometry in the range 60 to 68 wt pct Zn with a cubic structure has been reported by Kuz'ma et aL4 The YbzZn17, YbZn,,, and YbZn13 compounds have been reported by both Kuz'ma et a1 and Iandelli and Palenzona.' YbnZn17 has also been identified by Laube. This investigation was undertaken to establish the phase diagram of this system. Ytterbium in many respects behaves as an alkaline earth rather than a rare earth metal6 and it is of interest to note the resemblance between the Yb-Zn system, the Ca-Zn,' and typical rare earth-zinc systems.g'10 MATERIALS AND EXPERIMENTAL PROCEDURES The materials used in this investigation were Ames Laboratory ytterbium and Bunker-Hill slab zinc, 99.99 pct pure. Analyses of the ytterbium showed 38 ppm Ta, 82 ppm 0, and 15 ppm N with Ca, Cu, C, Mg, Al, Si, Cr, Fe, Ni, Sc, Y, Er, Tm, and Lu all less than 50 ppm. The ytterbium was dehydrogenated by heating in tantalum under vacuum for 8 hr at 900°C. The metal was kept under argon except when being cut with shears and when being weighed. Tantalum was found to be a suitable container for alloys in the composition range between ytterbium and Yb2Zn17. With higher zinc concentrations the tantalum was penetrated by the alloy and failed after several days at temperatures of 600" to 700°C. Approximately 20 g of zinc and ytterbium metal were sealed under argon in *-in.-diam tantalum cruci- bles equipped with thermocouple wells. The crucibles were in turn sealed in stainless-steel jackets. The alloys were equilibrated in an oscillating furnace and given various heat treatments in a soaking furnace. The steel jackets were removed and differential thermal analysis data were obtained under an atmosphere of argon. The thermal analysis apparatus was calibrated against the melting points of pure zinc, aluminum, silver, and copper and found to give thermal arrests within 1°C of the accepted melting temperatures for these elements. The thermal analysis apparatus has been described in an earlier paper.g Alloys were further heat-treated as necessary and subjected to metallographic examination and X-ray diffraction analysis. Most alloys were etched with Nital (0.5 to 10 pct nitric acid in alcohol). EXPERIMENTAL RESULTS The results of the thermal analysis are summarized by the points on the phase diagram, Fig. 1. Six compounds and five eutectics were observed. The eutectic temperature and compositions in weight percent zinc are 491°C and 12 pct, 645°C and 32 pct, 687°C and 54 pct, 742°C and 67 pct, and 750°C and 77 pct. The compounds YbZn, YbZn2, Yb2Zng, Yb2Zn17, and YbZnll melt congruently at 650°, 751°, 75Z°, 754", and 755"C, respectively. The compound Yb3Znll undergoes a peritectic decomposition at 695°C. The transformation and melting temperatures for the ytterbium were observed to be 797" and 817°C. re-

Jan 1, 1969

By J. N. Ong

The oxidation of tantalum is assumed to occur by four simultaneous first-order chain reactions; solution of oxygen in the metal, nucleation and growth of a suboxide phase at the metal surface and two phase boundary processes which give rise to two different modifications of Ta2O5. A rate equation is then formulated which accounts for all principal details of oxidation behavior, unifies and correlatss the results of the principal investigations, and expresses the rate as a function of pressure, temperature, and time. For purposes of practical application, the expressions: may be used below and above 700T respectively to determine the regression rate of tantalum in cm per hr, where T is to be expressed in "K and P in atmospheres pressure of oxygm. The equations will reproduce within a factor of two all reported experimental rates in the temperature range 475" to 1400°C and pressure range 0.000026 to 40.8 atm 0. 1 HE oxidation kinetics of tantalum have been investigated thoroughly in the temperature range 50" to 1400 and pressure range 1.32 x l0-' to 40.8 atm pressure of 0,and as a result, the principal features of the oxidation of tantalum are known and have been described in considerable detail. The exposition of the characteristics of the behavior of tantalum in oxygen has been largely descriptive, with considerable attention being devoted to elucidating the structure, composition, and morphology of the resulting oxide products. The weight change vs time results have usually been reported graphically. With the exception of the linear rate below 700 C and the process of diffusion of interstitial oxygen into the metal,6'9 no effort has been made to characterize the reaction rates in functional form. It is the purpose of this paper to demonstrate that when the fundamental principles of chemical kinetics are rigorously followed, the results of the principal investigations will be correlated and unified and the oxidation rale may be expressed as an analytic function of pressure, temperature, and time. In addition to accounting for the temperature and pressure dependency of the oxidation rate, the following minor features will be accounted for as a result of the basic analysis: the initial period of nonline-arity in rate at low temperatures, which decreases with increasing temperature;3'5'7 the rate vs temperature cusps obtained at constant pressure"5 the concentration gradient of oxygen interstitially dissolved in the metal.5'7 The analysis will also be consistent with the overall chemistry of reaction and with all visual, microscopic, and X-ray observations. DEVELOPMENT OF RATE EQUATION As a fundamental basis for the treatment of metal-oxygen reaction kinetics, it will be regarded that the rate of reaction is determined by the concentration and not the activity or chemical potential. It is further assumed that all metal-oxygen reactions are first order complex chain reactions" whose rate is dependent on the concentration of an intermediate species which is a complex function of the oxygen concentration, or oxygen pressure, only. The basic rate equation is therefore: is the weight of oxygen consumed by the reaction, A is that portion of the area of the metal over which the reaction is occurring (cm2), t the time (sec), kf the rate constant for forward reaction, C the intermediate species concentration and f '([Oz]) and f (Po,) are complex functions of oxygen concentration and Oxygen pressure respectively. Reverse reactions may usually be neglected in metal-oxygen systems since a large negative free energy generally accompanies these reactions. Eq. [I] takes different forms when the rate of reaction is controlled by diffusion into or through a phase or at a phase boundary. For diffusion into the metal phase, the rate is given by1' Di is the diffusion coefficient of species diffusing into the metal phase (cm2/sec), and Q is the corre-

Jan 1, 1962

By R. F. Steigerwald

The effects of heat transfer on the corrosion behavior of type 304 stainless steel in boiling water have been studied. Heat transfer conditions increase the tendencies of the stainless steel toward stress-corrosion mucking when the water is contaminated with Cl-. Surface preparation is the most important variable in determining the severity of the stress-corrosion problem in water with a given Cl- content. Heat treatment, chemical cleaning, and degree of wet film boiling also affect the corrosion of stainless steels used as heat transfer surfaces in boiling water. An up-paratus for corrosion testing under controlled heat transfer conditions is described. THE principal objective of this investigation was to study the corrosion behavior of AISI Type 304 stainless steel in boiling high-purity water under conditions of heat transfer. The principal variables in the study were: a) boiling conditions: limited boil, agitated boil; b) metallurgical structure: annealed or sensitized; c) surface condition: rolled, pickled, or ground. The results of the study should elucidate the role of heat transfer in the corrosion of stainless steel in boiling high-purity water and provide a base line from which to assess the severity of this type of corrosion. Although there has been an investigation of the effect of heat transfer on the corrosion behavior of stainless steels in alkaline waters,' work on the corrosion of stainless steels under heat transfer has been largely confined to various acid solutions.'-4 Furthermore, the study of the corrosion of stainless steels in high-purity water has been generally restricted to auto-clave and instream testing in superheated (e.g., 300°C) water and steam.5'6 Cooling water problems led to this study of the corrosion behavior of type 304 stainless steel in high-purity water at its atmospheric boiling point. In addition to the effects of heat transfer, this study also considered the influences of the type of boiling,7 metallurgical structure, and surface condition on the corrosion behavior of stainless steel in high-purity water. Two boiling conditions were investigated in this study: a) limiting boiling, i.e., when the heat-transfer surface had just reached the boiling point and boiling nucleated randomly over the specimen surface and b) agitated boiling, i.e., when a mild degree of superheat had been achieved on the specimen surface and boiling occurred generally over the specimen surface. Both boiling conditions are broadly classified as wet-film boiling. Originally, this program included the study of a third type of boiling, dry-film conditions. At dry-film boiling the temperature of the heat transfer surface is high enough so that it is covered with a continuous film of steam. Experimental difficulties made it impossible to study this kind of boiling with the available apparatus. Since surface condition affects heat transfer rates, three typical surfaces were chosen for study: a) as-rolled, the 2B finish received from the supplier, b) as-pickled, 30 min in 8 pct HNO3-1 pct HF, and c) as-ground on 120 grit paper. In order to evaluate the effect of improper heat treatment or welding on hot wall corrosion, both annealed and sensitized mi-crostructure were included in this study. EXPERIMENTAL Test Apparatus. The particular problems of interest in this investigation required a knowledge of the thermal gradient through the test specimen. From this gradient, the heat flux to the surface and the surface temperature could be determined. In order to satisfy this need, an apparatus similar to the boiling-disk apparatus of Fisher and whitney2 was designed. The solution is contained in a thermally-insulated, steel pipe lined with TEFLON resin. A stainless steel _______;________________________________________

Jan 1, 1970

By O. C. Ralston, F. Fraas

VIRTUALLY all commercial use of electrostatic separation has employed separators depending on differences of conductance of the broken, solid mixtures treated by them. The two main types of conductance separators have been: (1) Those in which the separating field is as near a static field between two charged electrodes as it is possible to maintain in the face of the usual leakage that takes place between electrodes with some 5 to 50 kv tension between them and spacing of 1/2 to 3 in.; (2) those in which a convective discharge of corona or spray type, but not a spark discharge, takes place between the carrier electrode and a charged electrode facing it, which is of very restricted area, such as a row of needle points or a small diameter wire parallel to the face of the carrier electrode. The present paper deals with this latter type. The principle is usable in separators where the carrier electrode, usually grounded, has the shape of a roller, a conveyor belt, a vibrating table, a sloping chute, or a nearly vertical plate. The innovation studied by us has been the use of the convective field for charging material on the carrier electrode and succeeded by a field between the carrier electrode and an electrode made of a true dielectric which cannot take on a charge by conduction but is charged by being in the radius of the corona discharge. The acquired charge is of the same sign as that of the corona but is not dischargable by contact with a good conductor. However, high-tension charge tends to leak off because of the ionization of the ambient air. The field between this electrode and the carrier electrode is as near static as it is possible to obtain. There are some differences in behavior of this electrode and that of the gas tube electrode used by Sutton, as will be discussed below. Both electrodes cause increased adhesion of nonconductive particles to the carrier roll. The particles are pinned there because they are convectively charged on their outer surfaces facing the corona electrode. The electrodes also cause increased rate of release of conductive particles tending to be pinned by corona charging but conveying the charge to the grounded carrier roll almost as rapidly as it is received by the particles. The sign of the potential on the corona-emitting electrode makes little difference in the separation. An electrode usually emits negative corona somewhat more easily than it emits positive corona, as electrons are then the fundamental particles emitted. With a positive electrode the flow of electrons involved in positive corona discharge is onto the electrode from the ambient gas. Theory In the separator illustrated in fig. 1, the nonioniz-ing electrode is a rotating, nonconductive dielectric cylinder designated as B. The ions emitted by the corona electrode, or wire F, charge both the particles on the carrier electrode, or roll A, and the surface of the dielectric electrode B. Whereas the space between roll A and wire F contains ions, the space between electrode B and roll A is a pure static field free of ions. The dielectric electrode has been described by Bullock.1 However, the corona electrode, which Bullock uses for the purpose of charging only the dielectric electrode, is adapted here to also charge the particles on the carrier roll. In operation the ionic field from the corona electrode is balanced with the static field from the dielectric electrode. The ionic field charges the particle so that it adheres to the roll. The static field intensifies the discharge of the corona charge by interfacial conduction and permits the release of the particle. The ionic and static fields therefore have opposing effects.2 The values of both fields are adjusted so that the poor conductor will adhere and the good conductor will be released.

Jan 1, 1951

By A. T. Corey, J. H. Henderson, M. R. J. Wyllie, C. H. Rathjens

The results of three-phase relative permeability tests on nine water-wet consolidated Berea sandstone samples are presented as composite ternary diagranls showing isoperms of oil, water and gas. Capillary pressure control was exercised over the flow of gas and oil in the presence of water. The water saturations ranged from 17 to 71 per cent pore volume. A method of calculating both the oil and water permeabilities of a three-phase system from the easily measured gas relative permeability is presented. EXPERIMENTAL PROCEDURE AND RESULTS A renewed interest has been shown in three-phase relative permeability as a result of recent developments involving underground combustion processes, steam injection, and other multiphase displacement processes. The experiments and results described here involved simultaneous flow of oil and gas in consolidated Berea sand with brine present as the wetting phase. Gas and oil relative permeabilities were measured on nine cores with CaC12 brine present as the wetting phase in saturations ranging from 17 to 71 per cent. The average residual liquid saturation of the cores was approximately 20 per cent. In order to make certain that brine was the wetting phase, the test cores were saturated with brine before contact with hydrocarbons. As an added precaution to avoid having oil displace brine from the wetting position as a result of changing wettability, each core was only used twice, i.e., first with a fixed percentage of brine and then for a gas-oil permeability determination with no brine present. The results, therefore, are presented as composite ternary diagrams representing the flow tests on nine individual cores having very similar properties. All tests were made using a modification of the capillary pressure techniquc described elsewhere. The effective oil permeability was measured before gas was introduced using a very small pressure gradient (a few centimeters of oil). This determination was made without selectively wet barriers in contact with the core. The cores were then placed between capillary barriers and gas-oil relative permeability curves obtained. The capillary barriers had been made water repellent with a silicone treatment. In determining gas-oil-water relative permeability in this fashion, control was exercised over the capillary pressure existing between the gas and oil. No control was exercised over the pressure difference existing between the oil and water. Athough an equal pressure gradient was applied to the gas and the oil phases, this pressure gradient does not exist in the water phase. Since the pressure gradient across the core was always much less than the displacement pressure of the fully saturated core, the pressure gradient can have caused only a very slight distortion of the oil-water interfaces. This slight distortion of the oil-water interfaces had a negligible effect on the validity of the oil permeabilities measured. The oil permeability, measured in the presence of water but with no gas present, was in every case equal. within experimental error, to the gas permeability of the gas-oil system when the oil saturation was the same as that of the water. Gas and oil relative permeabilities were plotted as a function of total liquid saturation. It was found that the gas relative permeability curves obtained on cores with brine present were identical with those obtained on the same cores with no brine present. The denominator for calculating oil relative permeabilities was the permeability found by extrapolation to infinite mean pressure (A la Klinken-berg). Fig. 1 illustrates gas-oil relative permeability results obtained on a typical core. The solid permeability curves represent the experimental data. The dashed oil relative permeability curve was calculated using the relationship;

Jan 1, 1957

By O. C. Ralston, F. Fraas

VIRTUALLY all commercial use of electrostatic separation has employed separators depending on differences of conductance of the broken, solid mixtures treated by them. The two main types of conductance separators have been: (1) Those in which the separating field is as near a static field between two charged electrodes as it is possible to maintain in the face of the usual leakage that takes place between electrodes with some 5 to 50 kv tension between them and spacing of 1/2 to 3 in.; (2) those in which a convective discharge of corona or spray type, but not a spark discharge, takes place between the carrier electrode and a charged electrode facing it, which is of very restricted area, such as a row of needle points or a small diameter wire parallel to the face of the carrier electrode. The present paper deals with this latter type. The principle is usable in separators where the carrier electrode, usually grounded, has the shape of a roller, a conveyor belt, a vibrating table, a sloping chute, or a nearly vertical plate. The innovation studied by us has been the use of the convective field for charging material on the carrier electrode and succeeded by a field between the carrier electrode and an electrode made of a true dielectric which cannot take on a charge by conduction but is charged by being in the radius of the corona discharge. The acquired charge is of the same sign as that of the corona but is not dischargable by contact with a good conductor. However, high-tension charge tends to leak off because of the ionization of the ambient air. The field between this electrode and the carrier electrode is as near static as it is possible to obtain. There are some differences in behavior of this electrode and that of the gas tube electrode used by Sutton, as will be discussed below. Both electrodes cause increased adhesion of nonconductive particles to the carrier roll. The particles are pinned there because they are convectively charged on their outer surfaces facing the corona electrode. The electrodes also cause increased rate of release of conductive particles tending to be pinned by corona charging but conveying the charge to the grounded carrier roll almost as rapidly as it is received by the particles. The sign of the potential on the corona-emitting electrode makes little difference in the separation. An electrode usually emits negative corona somewhat more easily than it emits positive corona, as electrons are then the fundamental particles emitted. With a positive electrode the flow of electrons involved in positive corona discharge is onto the electrode from the ambient gas. Theory In the separator illustrated in fig. 1, the nonioniz-ing electrode is a rotating, nonconductive dielectric cylinder designated as B. The ions emitted by the corona electrode, or wire F, charge both the particles on the carrier electrode, or roll A, and the surface of the dielectric electrode B. Whereas the space between roll A and wire F contains ions, the space between electrode B and roll A is a pure static field free of ions. The dielectric electrode has been described by Bullock.1 However, the corona electrode, which Bullock uses for the purpose of charging only the dielectric electrode, is adapted here to also charge the particles on the carrier roll. In operation the ionic field from the corona electrode is balanced with the static field from the dielectric electrode. The ionic field charges the particle so that it adheres to the roll. The static field intensifies the discharge of the corona charge by interfacial conduction and permits the release of the particle. The ionic and static fields therefore have opposing effects.2 The values of both fields are adjusted so that the poor conductor will adhere and the good conductor will be released.

Jan 1, 1951

By H. I. Aaronson, S. Toney

When the component grains of .ferritic hicrystals of an Fe-1.55 pct Si alloy are disoriented through an angle "6 " about a conzmon [ll0] axis, the tendency for preferential growth of austenite crystals along the grain boundary during transformation at elevated temperatures is small when 11 deg, but increases rapidly at larger angles. This type of orientation-dependence indicates that grain boundary diffdsion promotes preferential growth along large-angle boundaries. Morphological differences between austenite crystals formed at small-angle [1101 and [loo] boundaries suggest that precipitate morphology can be dependent on the dislocation structure of the boundary. ThE morphology of precipitate crystals nucleated at a grain boundary can be significantly affected by the structure of the boundary.' The limited amount of experimental evidence available in the literature indicates that the morphological effects of boundaries made up of arrays of dislocations, such as subbound-aries and small-angle grain boundaries, are different from those of boundaries having essentially disordered structures, i.e., large-angle grain boundaries. On the basis of indirect evidence, it has been concluded that large-angle grain boundaries give rise to the formation of grain boundary allotriomorphs (crystals which nucleate at grain boundaries, and grow preferentially and more or less smoothly along them)2 in the proeutectoid ferrite and the proeutec-toid cementite reactions in plain-carbon steels, and apparently also in many non-ferrous alloys.' At small-angle grain boundaries in a plain carbon steel, on the other hand, ferrite crystals were found to take the form of primary side plates. Similarly, Guinie, loys. Primary sideplates formed at a subboundary with a constant orientation tend to be parallel to only one, or occasionally two matrix habit planes, and a marked change in the orientation of the boundary is accompanied by a change in the habit plane. Previous studies on the morphological effects of grain boundary structure were performed on poly-crystalline aggregates. Information on the disorien-tation of the pairs of grains forming the boundaries at which the various morphologies appeared in these specimens was largely either qualitative or semi-quantitative. Precipitate morphologies accordingly could not be accurately and systematically correlated with grain boundary structure, and thus theories which have been proposed for the various morphological effects could not be satisfactorily tested. This investigation was undertaken in an attempt to remedy these deficiencies by studying the morphological effects of grain boundary structure with a method in which the boundaries are formed by matrix grains whose disorientations are known and controlled with reasonable accuracy. EXPERIMENTAL PROCEDURE The crystallographic requirements of this study were fulfilled by means of oriented bicrystals of silicon-iron. Disorientation of the component ferrite crystals was carried out about common, major crystallographic axes through angles ranging from 1/2 to 44 deg. The silicon content was low enough SO that the bicrystals could be partially transformed to austenite by heating to elevated temperatures. The silicon-iron used had the following initial composition: 1.55 pct Si, 0.04 pct C, 0.0031 pct N, 0.17 pct Mn, 0.020 pct S, and 0.002 pct P. The alloy was obtained in the form of 0.036-in. sheet. The procedures employed to prepare seed crystals in strips of this sheet, to reorient the seeds, and to grow them into bicrystals are essentially those described by Dunn and Nonken and aynes." The characteristics of the bicrystals are given in Table I. The "bicrystal type" indicates the crystallographic plane parallel to the broad faces of the strip in both grains and the crystallographic direction which was parallel to the long edges of the strip in both grains prior to disorientation. The angular disorientation of the grains, 8, which was performed about the direction normal to the plane of the broad faces of the strip, was measured between the [ 00l] directions. Orientation of the grain boundary, , was taken as the angle between the plane of the grain boundary and a plane containing the axis of disorienta-

Jan 1, 1962

By J. M. Roberts, N. Brown

The stress-strain behavior of zinc single crystals was measured over a strain range of 10-6 to 10-2. The phenomenon of macroyielding was observed in detail and plastic strains were detected at almost zero-stress. Closed hysteresis loops were observed during loading and unloading in the strain region of about 10-5. From the hysteresis a frictional stress on the dislocation of about 6 psi was obtained. A preliminary analysis indicates that impurities are primarily responsible for the friction. Nonelastic Strains as much as 10 -4 were recovered depending on the amount of prior deformation. Part of the recovered strain occurs instantaneously upon unloading and the remainder occurs at zero stress. The time dependence of the recovered strain was measured. THIS investigation is concerned with the details of plastic deformation preceding the ordinary yield point as measured with the usual strain sensitivity of about 10-4. The approach leads to internal friction observations in the hitherto neglected frequency range below 10-1 cycles per sec. It is believed that if the phenomenon of macroscopic yielding is to be understood, then the stress-strain curve in the neighborhood of the macroyield point should be greatly magnified. It may then be possible to determine whether macroscopic yielding is a unique event or whether it is a process which begins gradually at a lower stress. In the case of low-carbon steel a unique event obviously occurs at the macroscopic yield point as indicated by a drop in the load, but copper appears to exhibit a gradual transition from the elastic to the plastic state. In zinc the yield point is rather abrupt although the data indicates that some plastic deformation precedes large scale yielding.' One of the purposes of this investigation is to determine whether there is an abrupt transition from the preyield microstrain region to the region of macroscopic deformation. Such a rapid transition would support the concept that there is a critical stress for yielding. The concept that yielding is a unique event associated with such phenomenon as activating a Frank-Read source, freeing the dislocation from solute atoms, dislocations cutting through dislocations, or dislocations moving freely by one another, has been expounded widely on theoretical grounds. It is hoped that highly sensitive measurements of strain in the neighborhood of the macroscopic yield point will shed some light on the event known as the "Yield Point". EXPERIMENTAL METHOD 1) Specimens—High-purity zinc was cast into spherical graphite moulds in air and grown into spherical single crystals by the Bridgman method under a positive pressure of Argon gas. Spectro-graphic analysis of cleaved sections from four crystals showed a purity of 99.994 pet Zn. The specimens were acid machined with an 1/8 in. gage section in a form similar to those used by Parker and co-workers.2 Bausch type grips were fastened to the specimen by Epon VI adhesive. The specimens were oriented so that only [1120] (0001) slip occurred. Fig. 1 shows two of the specimens in the grips. Prior to each test, the gage section of the specimen was given a concentrated HNO3 chemical polish followed by alcohol rinsing and air blast drying. 2) Test Method- The shear tests were performed on an Instron testing machine and the experimental set-up was made very "hard". Strain could be measured to a sensitivity of 10 -6 by means of a capacitance gage extensometer. The design and calibration of this type of extensometer to measure microstrain, as applied to pure shear and tensile tests of metals, will be the subject of a separate paper—therefore, only a brief account will be presented here. The method essentially consists of attaching a

Jan 1, 1961

By S. R. B. Cooke, H. S. Choi, D. H. Harraway, I. Iwasaki

The mineralogy of natural iron ore samples and their slimes have been investigated and the nature of slime interference in iron ore flotation has been studied. The results have been correlated with the flotation behavior of a natural ore sample. Various conclusions have been reached as a result of these studies. In the flotation of iron oxide ores, desliming is generally considered to be an essential step to successful separation, irrespective of whether the iron oxide or siliceous gangue minerals are to be floated, although some workers have found empirically that certain collectors and reagent combinations are less sensitive to the presence of slime than others. The detrimental effect of slime is considered to be twofold. First, the presence of slime presupposes a high reagent consumption because of high specific surface. When clays are present and when cationic collectors are used abstraction by ionic exchange may augment this condition. Attempts to compensate by the addition of large amounts of reagent result in only partial correction. Second, slime coatings on granular particles tend to interfere with the bubble-mineral contact. The nature of slime coatings in flotation is quite complex and has been the subject of considerable study; an attempt was recently made by Fuerstenau et al.' to relate the slime-coating density with flotation recovery and with the properties of the electrical double layer at the mineral surfaces. Although major constituent minerals in the oxidized iron ores of the Mesabi and Cuyuna ranges are hematite and goethite (limonite) as the iron oxides, and quartz and chert as the siliceous gangue, very little is known of the mineralogy and of the chemical and physical characteristics of the slimes, and still less of the interaction between slimes, collector, and the mineral surfaces. For pragmatic reasons iron ore slimes are defined as — 20p material, based upon the calculated settling velocity of a quartz sphere of the stated diameter, and of all other equal-settling mineral particles. Active slime interference with flotation is usually attributed to particles 5p in size or finer, the extent of such interference appearing to depend not only on the mineralogy but also on the size distribution of each mineral in the slime fraction. The objective of this work was to acquire a more specific knowledge of the constitution of iron ore slimes and of their role in flotation. The mineralogi-cal composition of natural slimes was obtained by differential thernal analysis (hereinafter referred to as DTA), electron microscopy, and chemical and X-ray analyses. Some flotation tests were made on natural ore samples. The surface properties of several constituent minerals were investigated by electrophoretic measurements and by determination of the adsorption of some typical flotation collectors. Finally, simplified flotation tests were made on granular goethite and quartz in the presence of various artifically prepared slimes; the results were compared with laboratory flotation tests made on natural ores. MATERIAL AND METHODS Mineralogy of Some Iron Ore Slimes: Samples of two wash-ore tailing::, hereinafter identified as A* and B, *Sample A of the present investigation 18 the same am ore A in ref. 3. of a wash ore C, and of a paint rock D, all from the Mesabi range, were selected for investigation on the basis of prior information concerning their flotation behavior. The two wash-ore tailings, when deslimed, were known to respond well to flotation, whereas the wash ore was high in goethite, tended to be slimy, and responded poorly to flotation. The paint rock also exhibited sliming tendencies, and was suspected to contain relatively large quantities of clay minerals because of its high A1203 content. Gruner states that the paint rock of the Mesabi frequently contains kaolinite. To ascertain the relative sliming tendencies of each sample a standardized desliming method was employed. All samples were ground through 65 mesh using jaw and rolls crushers. A 500-g sample of each

Jan 1, 1962

By C. N. Reid

Slip-line studies on deformed chromium single cvystals showed the usual bcc behavior. At room temperatuve, cross slip was prevalent—slip was not confined to a given plane, but the slip direction was (111). At -10O0K, slip occuvred on (110) planes, twins on(112) planes, and cleavage on (1001 planes. A single-crystal tensile specimen with an axis close to [011] showed a pronounced yield drop and high strain rate sensitivity which zclere used to derive relevant parame tevs in a dislocation dynamics treatment. Transmission electron microscope studies confirmed the existence of (110) slip planes and showed ecidence of loops punched out by precipitates and of grown-in dislocations promoting tangling. OF recent years experimental studies have been made of the deformation characteristics of single-crystal molybdenum and tungsten, but very little has been published on the behavior of single-crystal chromium. During a study of the mechanical properties of chromium, single-crystal studies were made which have already been partially described.&apos; However, additional information was generated which was not directly relevant to the main theme of Ref. 1, and, therefore, was not reported. In view of the need for complete documentation of deformation modes, the experimental observations made on the deformation of single-crystal chromium are summarized here, together with an electron-microscope study of the associated dislocation structures. It was found that, in terms of the deformation modes, chromium is a conventional bcc metal, showing a very pronounced yield-point phenomenon. Further, it was found that the flow strength of these crystals is very sensitive to the strain rate. Finally, the crystals were observed to contain many unidentified precipitates, which often were associated with prismatic dislocation loops. EXPERIMENTAL METHODS Single crystals were grown from rods of wrought chromium by the method of zone annealing. Rods of "1/4in.-diam were supported vertically in an argon atmosphere while an induction coil was moved up the rod at 1 in. per hr. The power was adjusted to just below that required for melting, and the process produced single crystals in about 30 pct of the rods used. The orientations of the crystals, in general, lay near [011] and are summarized in Fig. 1. Before this treatment, the wrought material contained 35 pprn C, 68 ppm O, and 12 ppm N.* An analyzed single crystal *Usual metallic impurities found in iodide chromium are: Al, 5 ppm; Ca, A ppm; Cu, 2 ppm; Fe, 75 ppm; Yg, 0.5 ppm; Yn, < 3 ppm; Mo, < 3 ppm; Ni, 4 ppm; Si, < 20 ppm; Ti, < 1 ppm; V, 4 ppm; Zr, < 3 ppm. contained 10 pprn C, 79 ppm O, and 50 pprn N. Tension and compression specimens were shaped from the crystals by mechanical grinding, followed by the electrolytic removal of about 0.010 in. from the surface in a perchloric/acetic acid bath. All specimens had a gage length of 0.75 in., and tension specimens had a diameter of 0.100 in., while that of the compression samples was 0.200 in. Mechanical tests were carried out at a rate of 1.3 pct per min, and temperatures below 0°C were attained by means of a nitrogen cryostat similar to that of Wessel.2 EXPERIMENTAL RESULTS Modes of Deformation. In addition to the tensile properties of these crystals, which are described in Ref. 1, deformation markings on the surface were studied. Crystals A and F, Fig. 1, were deformed in tension at 300°K to 10 and 16 pct strain, respectively. The surfaces contained visible slip lines, about 1 C( apart, composed of both straight and wavy segments. They did not define a single plane, and so determination of the slip plane was not possible. However, the slip direction was deduced by comparing the axial orientations of the crystals before and after deformation. Fig. 2 is representative, and shows that the axis ro-

Jan 1, 1968

By Orville R. Lyons

THE relative performance of coal washing equipment, or the effectiveness with which any type or make of equipment removes impurities from coal, has been most difficult to evaluate in the past. The most widely used yardstick is the Frazer and Yancey efficiency formula developed in 1922,1 but Yancey in a later article states that "washers treating coals of different density composition or operating at different densities of separation cannot be compared directly on the basis of this criterion."&apos; Prior to and since 1922, a variety of other methods has been used for comparison purposes, including the distribution curve, the error area, and the "ecart probable" or probable error. Yancey and Geer in discussing these methods conclude, "Performance can be evaluated in a number of different ways, with the choice of the proper method to use being dictated by the objectives of the investigation and the data available."&apos; It is true that performance can be evaluated in a variety of ways, but if the equipment is to be evaluated on an effectiveness basis, there should be only one universal comparison method. Varying methods have been used because one universal comparison method has not been found or developed. In the article previously quoted, Yancey and Geer state in clear terms the primary concept for a universal comparison method: "One of the simplest, and certainly one of the most obvious evaluations of washery performance is the quantity of sink material in the washed coal and the float material in the refuse. If the washery products are tested at the density at which the washing unit is operated, the sink in the washed coal and the float in the refuse represent material that has been misplaced." The quantity of misplaced material was used as a criterion of washery performance by Lincoln in 1913,8 by the United States Bureau of Mines in 1938,4 by Hancock in 1947,3 and by the national French research agency Cerchar in recent years.2 In 1950 Anderson&apos; proposed the use of this criterion as an efficiency value to replace the Frazer and Yancey formula. However, none of the above-mentioned investigators used the misplaced material concept in a manner that would provide universal coal-cleaning equipment comparisons. The Correlation Theory The ideal coal cleaning process would treat all sizes and would make a perfect separation at any given specific gravity. All material lower in density than the desired value would report in the coal product and all material higher in density would report in the refuse product. Unfortunately, no known cleaning process achieves this goal and there seems little likelihood that any process yet to be invented will do more than approach it. When coal is treated in volume under operating conditions, it is impossible to avoid mechanical entrapment, fluctuations in throughput and effective gravity of separation, and the creation of turbulent currents, even when a true heavy-liquid bath is used and the feed is closely sized and contains little intermediate gravity material. This being so, it is possible to appreciate the difficulties inherent in trying to obtain a perfect separation when treating a wide range of sizes and a feed containing high percentages of intermediate material, using turbulent currents to help create the effective separation gravity, under operating conditions which normally tend to be on the overload side. When coal is separated from refuse in any coal cleaning equipment, some refuse always reports to the coal and some coal to the refuse; the writer therefore assumed that there should be a relationship between the total amount of misplaced material produced by any given piece of equipment and the difficulty of separation as represented by the percentage of near gravity material in the feed. With small amounts of near gravity or ±0.1 material in the feed there should be less misplacement of material than would occur with large amounts of near

Jan 1, 1952

By J. H. Schulman, M. H. Buckenham

Although much interest has been taken in the use of mixed collectors in flotation, this investigation is probably the first in which oppositely charged collectors have been considered. The results obtained and the techniques used could well be applied in the behavior of other mixe the behavior of other mixed collector systems and could possibly explain the effective flotation results which have been reported when various collector combinations have been used. Collectors conventionally employed in flotation systems are soluble in water, but many of their homologs of longer hydrocarbon chain length are insoluble. The properties and behavior of these insoluble compounds may be conveniently studied when they are spread as monolayers at the air/water interface on the Langmuir-Adam trough. Although some extrapolation is involved in applying effects observed at this interface to the solid/liquid interface where the action of collectors is most important in flotation, the technique nevertheless is most useful for the study and interpretation of flotation phenomena. Of particular interest in this field are investigations on the insoluble monolayers of the fatty acids, alkyl sulfates and alkyl amines; the penetration of these insoluble monolayers by soluble surface active components and their interaction with metal ions from the underlying solution.&apos;-&apos; Unfortunately, the insoluble xanthates and related compounds do not exhibit stable monolayer properties due to rapid oxidation at the air/water interface and, therefore, cannot be studied directly in this way. These approaches have enabled Leja and Schulman8 to suggest mechanisms explaining dynamic attachment of mineral particles to air bubbles involving collector-frother interaction and the adsorption of collectors onto mineral surfaces. In this and other papers 9-12 considerable evidence is presented to support the concept of collector-frother and metal ion-monolayer interaction and to emphasize the value of monolayer techniques in elucidating the flotation system. Molecular interactions resulting from monolayer penetration are determined by the nature of and the association between both the polar and nonpolar groups of the two molecules concerned. Stable complexes are formed on penetration when interaction takes place between both the polar and nonpolar groups, and although the resultant complexes are not necessarily true chemical compounds, the properties of the molecularly associated complexes are very different from those of the individual components. Shortening of, or changes from, a straight hydrocarbon chain in one of the reacting molecules reduces considerably the stability of the associated complex as do changes in temperature, pH and substrate composition. The effect of hydrocarbon chain length becomes most important when observed effects are to be applied in flotation studies where soluble homo-logs and, therefore, much shorter hydrocarbon chain lengths are used. The present investigation is based on Langmuir trough work carried out by Bowcott,l3 who studied the penetration of insoluble amine monolayers by potassium lauryl xanthate. Bowcott observed that cetyl amine monolayers were readily penetrated by xanthate, but found that with time the high film pressures resulting from penetration and association fell off, indicating decomposition and ejection of xanthate from the film. This decomposition was pH dependent. Of particular interest in this work were studies on an equimolecular mixed monolayer of the fully N-substituted ammonium compound, for example, cetyl trimethyl ammonium iodide (CTAI) and potassium cetyl xanthate. Despite the fact that the CTAI is water soluble and the xanthate on its own is incapable of forming a monolayer, the mixed film was stable up to a surface pressure of 67 dynes per cm. In this condensed state the xanthate was stabilized against atmospheric oxidation, although iodine injected beneath the film caused an immediate collapse. The stabilizing of xanthate against oxidation by association with an alkyl trimethyl ammonium bromide (TAB) could be important in flotation, and a study of the performance and behavior of mixed collectors therefore was undertaken. A modified Hallimond tube operated under controlled conditions was used to evaluate flotation. Surface tension measurements were made to investigate the properties of the soluble

Jan 1, 1963

By C. C. Martin, M. C. Fuerstenau, R. B. Bhappu

Experiments revealed that quartz could not be floated in conductivity water at any pH with a long-chained sulfonate as collector. Various cations, Fe+++, Al+++, Pb++, Mn++, Mg++, Ca++, are shown to function as activators when the pH is such that the cation hydrolyzes. As the solubility product of the various cation-sulfonates was exceeded at the concentrations involved, precipitated cation-hydroxy-sulfonates, e.g. Fe (RSO3)2OH must be functioning as the collector in these systems. A number of interesting and important phenomena were revealed during a study of the response of beryl to sulfonate flotation.&apos; Perhaps the most important observation is the effect of various cations on flotation response. Experiments showed that in the vicinity of pH 3.0, about three ppm Fe+++ increased recovery of leached beryl from about 60 pct to 100 pct, whereas about four ppm Ca+ + reduced the recovery from 60 pct to 2 pct. With the exception of ferric iron, all of the other cations investigated reduced flotation recoveries drastically at this pH. As postulated in the paper Sulfonate Flotation of Beryl,&apos; even with low concentrations of polyvalent cations and sulfonate (on the order of one ppm), cation-sulfonates are precipitated immediately in solution. That is, blueish-white clouds were noted to form after given additions of salts to known solutions of sulfonate. Furthermore, it was also shown that one-hundred-fold more ferric iron than necessary to form the precipitated cloud had to be added to effect complete flotation. In other words, some form of solid ferric sulfonate was found to function as the collector in these systems. The form of the compound was suggested to be Fe(RCO3)2OH and that bonding to the surface occurs through the hydrogen of the hy-droxyl. As the form of this compound was shown to be dependent on the extent of hydrolysis of ferric iron, it is to be expected that ferric iron will be unique in some pH region. Further, if the presence of hydroxyl in the neutral precipitated compound is of primary importance, then other cations should function similarly but at different values of pH, since they will hydrolyze at different concentrations of hydroxyl ion. To determine whether the premise of hydrolysis is correct, the study was extended to quartz systems in the presence of various cations at various values of pH. EXPERIMENTAL MATERIALS AND METHOD Sodium alkyl aryl sulfonate was chosen as the collector for the experimental work. The reagent, sup plied as a courtesy sample by the Shell Chemical Co., has the following physical properties: Physical form Solid — Finely ground Sulfonate content, pct wt 95 to 97 Molecular Weight 450 to 470 Number of carbon atoms in hydrocarbon chain 25 to 30 Melting Point, OF 250 to 260 Solubility Soluble in water with gel formation at concentrations higher than 25 pct by weight sulfonate This particular reagent was chosen because of its high active sulfonate content, long-chain length, and solid form. With the exception of the frother and sulfonate, all other chemicals were of reagent grade quality. Conductivity water was used in the experimental work. This water, made by passing distilled water through an ion exchange column, had an average measured conductivity of one micromho. Experiments were conducted at room temperature in a small glass flotation cell with the following procedure: 1) A redetermined amount of water and salt solution (e.g. CaC12 . 2H2O) were combined and the pH adjusted to a given value. 2) A given amount of sulfonate was added so that final solution volume was 130 cc. 3) One drop of Dow 250 frother was added. 4) Five g of quartz were added and the system conditioned for five minutes. 5) The pH of the system was measured (termed flotation pH).

Jan 1, 1963

By Murray F. Hawkins

Horner1 and van Everdingen8 ave shown that the pressure drop within the wellbore, as a result of having produced the well at a constant rate q for time t, where t is sufficiently large, is: van Everdingen observed that better agreement between theory and well performance can be obtained if, instead of assuming the permeability is kc everywhere about the well, it is assumed the permeability near the well-bore is substantially reduced as a result of drilling, completion and/or production practices. In order to account for the additional pressure drop he introduced the dimensionless quantity S, the skin effect factor, so that Eq. 1 becomes: Eq. 2 might have also been obtained as follows. Assume a zone of altered permeability k, exists about the well out to a radius r and beyond that the unaltered, external permeability k. The additional pressure drop required to overcome this skin of reduced permeability may be calculated with sufficient accuracy using the incompressible flow equation; for Browns-combe and Collins1 have shown almost no difference between compressible and incompressible steady-state flow, in the vicinity of the wellbore, and the small volume of fluid in the vicinity of the wellbore makes unsteady-state mechanics unnecessary. Then. The sign of this skin pressure drop will be positive or negative depending upon whether the altered permeability k, is smaller or larger, respectively, than the external permeability k... Adding the pressure drop of Eq. 3 to Eq. 1 to find the total pressure drop: Comparing Eq. 4 with Eq. 3 it is seen that the skin effect may be defined by: be determined from pressure build-up tests1,3,4,5,6,7,8 The average permeability kavg including the altered and external permeabilities, can be determined from PI tests, and may be defined approximately on the basis of steady-state flow, as was done by Thomas&apos; in defining the damage factor, by: The productivity ratio is the ratio of the average to the external permeability, kavg/ke or This equation shows that the productivity ratio and the skin effect are not uniquely related, because of the uncertainty in the drainage radius, and also, in many instances, the wellbore radius. Fortunately, they enter in the logarithm. The curves of Fig. I are plots of Eq. 8 for values from 100 to 50,000. The points represent the skin effects and corresponding productivity ratios from a large number of well tests, taken from Fig. 15 of Ref. 5 or Fig. 13 of Ref. 9. While some of the data

Jan 1, 1957

By W. R. Jones

composition, he cannot reasonably asl; the manufacturer to guarantee that this composition shall give certain physical results. W. R. Jones, Pittsburgh, Pa. : The question that naturally occlun to me is this: Has Dr. Dudley in his inveatigtrtions been aiming to prove a theory, or has he been guided by an earnest desire to discover what are the proper elements in the composition of a good-wearing steel rail ? Unfortunately, for correct chemical information, he has omitted in his analgw two very importnat elements,—sulpbur and copper. Now, before we will even begin to admit the correctnets of Dr. Dudley&apos;s conclusions and the formula he prescribes, we will at the start question the propriety of any chenlist or scientist prescribing a formula for making steel when he has iguared such important ele ments as sulphur aud copper. I, for one, will not accept any such formula. Are we sure, or is Dr. Daclley sure, that the chemical analyseq embodied in his paper are correct? This may seem a presumptuous queetion, yet, with my experience with chenlists, I naturally doubt the correctness of the analyse8, and, before I will accept them as correct, I will ask that comparative tests of phosphorous and man ganese be made by the Pennsylvania Railroad chemists and the chemists of the leading steel-works in the country. Let us first verify the correctness of the analyses before we consider the con clusions. I can enumerate a great number of instances in which chemists have differed very widely in their determinations of phos phorus and manganese. A prominent iron fitam made a contract with the Edgar Thomson Steel Company to deliver pig metal guar anteed to be between 0.07 and 0.08 phosphorus; an analysis by our chemist resulted in phosphorus 0.148 and 0.152,—a rather startling difference! Again, a sample bar of steel, in which our chemist reported phosphorus 0.11, was tested by a chemist of au other Bessemer works, ana his determinations were phosphorus between 0.07 and 0.08: A leading engineering establishmeut of Pittsbdrgh bought iron claimed by a chemical analysis to contain 0.08 phosphorus; our Mr. Ford found phosphorus 0.145. A chem ist connected with an open-hearth works reported manganese in a piece of steel, 1.14; in a second determination from the same piece of steel, by the same chemist, manganese was reported 0.43. The chemist was kept in ignorauce of the fact that both samples were from the saw piece of steel. Two dctermiuations for manganese

Jan 1, 1881

By B. A. Cheadle, C. E. Ells

The ovienlalion of hexagonal a-zirconium crystals in cold-drawn Zircaloy-2 tubes and in both as-extruded and heat-treated Zr-2.5 wt pcl ND tubes has been rrleasured using the inverse Pole - figure technique. Uniaxial tensile tests hare shown the Zil-caloy-2 lubes to hare highly anisotropic delovmation behavior whereas heat-treated Zr-2.5 wt pet Nb tubes are nearly isotropic. The differences in deformation behavior are esbloilred from the observed textures of the tubes and the deformation systems known to oberate in Zircnloy,-3. Tlze vcsults lead to an explanation of the high effective strain observed fov the Zircaloy-2 tubes as colrzpared to heat-treated Zr-2.5 wt pet Nb tubes in restrained end burst tests at 280° to 300°C. THE Zr-2.5 wt pct Nb alloy. when heat-treated by quenching from temperatures slightly below the (a + p)/P phase boundary and subsequently aged at 500°C, has tensile strengths about 50 pct greater than those of 20 pct cold-worked Zircaloy-2.1 There is. therefore, considerable economic incentive to replace Zircaloy-2 with the heat-treated alloy in some in-reactor applications. notably for pressure tubes, where strength is a prime consideration. However, when tubes of Zr-2.5 wt pct Nb fabricated by extrusion and drawing prior to heat treatment were subjected to restrained end-burst tests at 300 °C. the circumferential expansion at failure1 was only 10 pct that of cold-drawn Zircaloy-2 tubes in similar tests,2 Table I. This result was not predicted from uniaxial tensile tests in which the ductilities of the two materials were quite similar.&apos; The detailed requirement for ductility in pressure vessels has not yet been worked out. and comparison of the relative merits of cold-worked Zircaloy-2 and heat-treated Zr-2.5 wt pct Nb is further complicated by the irradiation-induced loss of ductility and hydrogen pickup each will undergo from reactor operation.1,2 Nevertheless. the lower circumferential expansion of the Zr-2.5 wt pct Nb tubes raised serious doubts on the advisability of their use as pressure vessels. For this reason, an investigation to determine the cause for different ductilities of the two types of tubes was initiated. From a study of uniaxial tensile properties and crystallographic orientation it has been found that the fracture ductilities observed in the burst tests can be related directly to the crystallographic ori-

Jan 1, 1965